Classifications

• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
  • G11B5/62—Record carriers characterised by the selection of the material
  • G11B5/68—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent
  • G11B5/70—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer
  • G11B5/706—Record carriers characterised by the selection of the material comprising one or more layers of magnetisable material homogeneously mixed with a bonding agent on a base layer characterised by the composition of the magnetic material
• • G—PHYSICS
  • G11—INFORMATION STORAGE
  • G11B—INFORMATION STORAGE BASED ON RELATIVE MOVEMENT BETWEEN RECORD CARRIER AND TRANSDUCER
  • G11B5/00—Recording by magnetisation or demagnetisation of a record carrier; Reproducing by magnetic means; Record carriers therefor
  • G11B5/62—Record carriers characterised by the selection of the material
  • G11B5/73—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer
  • G11B5/733—Base layers, i.e. all non-magnetic layers lying under a lowermost magnetic recording layer, e.g. including any non-magnetic layer in between a first magnetic recording layer and either an underlying substrate or a soft magnetic underlayer characterised by the addition of non-magnetic particles
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S428/00—Stock material or miscellaneous articles
  • Y10S428/90—Magnetic feature
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
  • Y10T428/256—Heavy metal or aluminum or compound thereof
  • Y10T428/257—Iron oxide or aluminum oxide

Definitions

• the present invention relates to a magnetic recording medium. More particularly, the present invention relates to a magnetic recording medium which uses the hematite particles as non-magnetic particles for a non-magnetic undercoat layer, and which has small light transmittance, smooth surface, high strength and high durability.
• magnetic recording media such as a magnetic tape and magnetic disk have been increasingly and strongly required to have a higher performance, namely, a higher recording density, higher output characteristic, in particular, an improved frequency characteristic and a lower noise level.
• the properties which magnetic particles are required to have in order to satisfy the above-described demands on a magnetic recording medium are a high coercive force and a large saturation magnetization.
• acicular magnetic particles containing as a main ingredient which are obtained by heat-treating acicular goethite particles or acicular hematite particles in a reducing gas are widely known.
• Video tapes have recently been required more and more to have a higher picture quality, and the frequencies of carrier signals recorded in recent video tapes are higher than those recorded in conventional video tapes. In other words, the signals in the short-wave region have come to be used, and as a result, the magnetization depth from the surface of a magnetic tape has come to be remarkably small.
• the surface roughness of a hardened magnetic layer depends on the surface roughness of the substrate (back surface roughness) so largely as to be approximately proportional, . . . , since the magnetic layer is formed on the substrate, the more smooth the surface of the substrate is, the more uniform and larger head output is obtained and the more the S/N ratio is improved.”
• the end portion of a magnetic recording medium such as a magnetic tape, especially, a video tape is judged by detecting a portion of the magnetic recording medium at which the light transmittance is large by a video deck. If the light transmittance of the whole part of a magnetic recording layer is made large by the production of a thinner magnetic recording medium or the ultrafine magnetic particles dispersed in the magnetic recording layer, it is difficult to detect the portion having a large light transmittance by a video deck.
• carbon black or the like is added to the magnetic recording layer. It is, therefore, essential to add carbon black or the like to a magnetic recording layer in the present video tapes.
• Non-magnetic undercoat layer comprising a binder resin and non-magnetic iron-based oxide particles such as hematite particles which are dispersed therein, on a non-magnetic substrate such as a base film
• Japanese Patent Application Laid-Open (KOKAI) No. 5-182177 (1993) discloses a magnetic recording medium comprising: a non-magnetic substrate; a non-magnetic undercoat layer formed on the non-magnetic substrate and produced by dispersing inorganic particles in a binder resin; and a magnetic layer formed on the non-magnetic undercoat layer and produced by dispersing ferromagnetic particles in a binder resin while the non-magnetic undercoat layer is wet; wherein the magnetic layer has a thickness of not more than 1.0 ⁇ m in a dried state, the non-magnetic undercoat layer contains non-magnetic inorganic particles with surface layers coated with an inorganic oxide, the inorganic oxide coating the surfaces of the non-magnetic inorganic particles contained in the non-magnetic undercoat layer is at least one selected from the group consisting of Al 2 O 3 , SiO 2 and ZrO 2 , and the amount of the inorganic oxide coating the non-magnetic
• Japanese Patent Application Laid-Open (KOKAI) No. 6-60362 (1994) discloses a non-magnetic undercoat layer for a magnetic recording medium formed on a non-magnetic substrate, comprising a coating composition containing non-magnetic particles and a binder resin; wherein the non-magnetic particles are non-magnetic particles constituted by acicular ⁇ -Fe 2 O 3 particles coated with an Al compound, and the non-magnetic particles constituted by acicular ⁇ -Fe 2 O 3 particles coated with an Al compound have an average major axial diameter of 0.05 to 0.25 ⁇ m, an average minor axial diameter of 0.010 to 0.035 ⁇ m, a particle size distribution of not more than 1.40 in geometrical standard deviation, and an aspect ratio (major axial diameter/minor axial diameter) of 2 to 20.
• non-magnetic particles are not particles which contain aluminum substantially uniformly from the central portions to the surfaces of the particles but particles which have an aluminum compound on the surfaces thereof.
• the above-described magnetic recording media composed of a non-magnetic substrate and a non-magnetic undercoat layer produced by dispersing non-magnetic particles in a binder resin and formed on a non-magnetic substrate, have a small light transmittance, a smooth surface and a high strength, but the durability thereof is inconveniently poor.
• magnetic iron-based metal particles As a result of studies undertaken by the present inventors so as to solve the above-described problems, it has been found that by using specific acicular hematite particles as non-magnetic particles for a non-magnetic undercoat layer of a magnetic recording medium and magnetic particles containing as a main ingredient (hereinafter refer to as "magnetic iron-based metal particles") as the magnetic particles for a magnetic recording layer of a magnetic recording medium, the obtained magnetic recording medium has small light transmittance, smooth surface, high strength and high durability.
• the present invention has been achieved on the basis of this finding.
• a magnetic recording medium comprising:
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and a binder resin;
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient and a binder resin.
• a magnetic recording medium comprising:
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and having a coating comprising at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon, which is coated on the surfaces of said acicular hematite particles, and a binder resin; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient and a binder resin.
• a non-magnetic undercoat layer for a magnetic recording medium having a magnetic recording layer containing magnetic particles containing iron as a main ingredient
• said non-magnetic undercoat layer to be formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and a binder resin.
• a magnetic recording medium comprising:
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and having an average major axial diameter of not more than 0.3 ⁇ m, an average minor axial diameter of 0.0025 to 0.15 ⁇ m and an aspect ratio of not less than 2:1, and a binder resin; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient and a binder resin.
• a magnetic recording medium comprising:
• a non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising a binder resin and non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles, having an average major axial diameter of not more than 0.3 ⁇ m, an average minor axial diameter of 0.0025 to 0.15 ⁇ m and an aspect ratio of not less than 2:1, and having a coating comprising at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon, which is coated on the surfaces of said acicular hematite particles; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient and a binder resin.
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and a binder resin;
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient containing 0.05 to 10% by weight of aluminum, calculated as Al, based on the total weight of the magnetic particles and a binder resin.
• a magnetic recording medium comprising:
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and having a coating comprising at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon, which is coated on the surfaces of said acicular hematite particles, and a binder resin; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient containing 0.05 to 10% by weight of aluminum, calculated as Al, based on the total weight of the magnetic particles and a binder resin.
• a non-magnetic undercoat layer for a magnetic recording medium having a magnetic recording layer containing magnetic particles containing iron as a main ingredient containing 0.05 to 10% by weight of aluminum, calculated as Al, based on the total weight of the magnetic particles, said non-magnetic undercoat layer to be formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and a binder resin.
• non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles and having an average major axial diameter of not more than 0.3 ⁇ m, an average minor axial diameter of 0.0025 to 0.15 ⁇ m and an aspect ratio of not less than 2:1, and a binder resin; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient containing 0.05 to 10% by weight of aluminum, calculated as Al, based on the total weight of the magnetic particles and a binder resin.
• a non-magnetic undercoat layer formed on said non-magnetic substrate, said undercoat layer comprising a binder resin and non-magnetic acicular hematite particles containing 0.05 to 50% by weight of aluminum uniformly within the particles, calculated as Al, based on the total weight of the non-magnetic particles, having an average major axial diameter of not more than 0.3 ⁇ m, an average minor axial diameter of 0.0025 to 0.15 ⁇ m and an aspect ratio of not less than 2:1, and having a coating comprising at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon, which is coated on the surfaces of said acicular hematite particles; and
• said magnetic recording layer formed on said non-magnetic undercoat layer, said magnetic recording layer comprising magnetic particles containing iron as a main ingredient containing 0.05 to 10% by weight of aluminum, calculated as Al, based on the total weight of the magnetic particles and a binder resin.
• the non-magnetic undercoat layer in the present invention is produced by forming a coating film on the non-magnetic substrate and drying the coating film.
• the coating film is formed by applying a non-magnetic coating composition which contains acicular hematite particles, a binder resin and a solvent, to the surface of the non-magnetic substrate.
• the non-magnetic substrate As the non-magnetic substrate, the following materials which are at present generally used for the production of a magnetic recording medium are usable: a synthetic resin such as polyethylene terephthalate, polyethylene, polypropylene, polycarbonate, polyethylene naphthalate, polyamide, polyamideimide and polyimide; foil and plate of a metal such as aluminum and stainless steel; and various kinds of paper.
• the thickness of the non-magnetic substrate varies depending upon the material, but it is ordinarily about 1.0 to 300 ⁇ m, preferably 2.0 to 200 ⁇ m.
• polyethylene terephthalate is ordinarily used as the non-magnetic substrate.
• the thickness thereof is ordinarily 50 to 300 ⁇ m, preferably 60 to 200 ⁇ m.
• the thickness thereof is ordinarily 3 to 100 ⁇ m, preferably 4 to 20 ⁇ m.
• the thickness thereof is ordinarily 3 to 50 ⁇ m, preferably 4 to 20 ⁇ m.
• the thickness thereof is ordinarily 2 to 10 ⁇ m, preferably 3 to 7 ⁇ m.
• the thickness of the undercoat layer obtained by coating the non-magnetic substrate with the non-magnetic coating composition and drying the coating film is ordinarily 0.2 to 10.0 ⁇ m, preferably 0.5 to 5.0 ⁇ m. If the thickness is less than 0.2 ⁇ m, not only it is impossible to ameliorate the surface roughness of the base film but also the strength is insufficient.
• the binder resin in the present invention the following resins which are at present generally used for the production of a magnetic recording medium are usable: vinyl chloride-vinyl acetate copolymer, urethane resin, vinyl chloride-vinyl acetate-maleic acid copolymer, urethane elastomer, butadiene-acrylonitrile copolymer, polyvinyl butyral, cellulose derivative such as nitrocellulose, polyester resin, synthetic rubber resin such as polybutadiene, epoxy resin, polyamide resin, polyisocyanate, electron radiation curing acryl urethane resin and mixtures thereof.
• Each of these resin binders may contain a functional group such as --OH, --COOH, --SO 3 M, --OPO 2 M 2 and --NH 2 , wherein M represents H, Na or K.
• a binder resin containing a functional group --COOH or --SO 3 M is preferable.
• the mixing ratio of the non-magnetic particles to the binder resin in the non-magnetic undercoat layer is ordinarily 5 to 2000 parts by weight, preferably 100 to 1000 parts by weight based on 100 parts by weight of the binder resin.
• the gloss of the coated film of the non-magnetic undercoat layer containing acicular hematite particles according to the present invention is ordinarily 170 to 280%, preferably 180 to 280%, more preferably 185 to 280%, even more preferably 190 to 280% and the surface roughness Ra thereof is ordinarily 1.0 to 15.0 nm, preferably 1.0 to 13.0 nm, more preferably 2.0 to 12.0 nm, even more preferably 2.0 to 10.0 nm.
• the Young's modulus (relative value to a commercially available video tape: AV T-120, produced by Victor Company of Japan, Limited) thereof is ordinarily 125 to 150, preferably 127 to 150, more preferably 130 to 150.
• the acicular hematite particles used in the present invention contain usually 0.05 to 50 wt %, preferably 0.1 to 30 wt %, more preferably 0.5 to 20 wt % of aluminum approximately uniformly within the particles (calculated as Al) based on the total weight of the non-magnetic acicular hematite particles.
• the average major axial diameter of the acicular hematite particles used in the present invention is ordinarily not more than 0.3 ⁇ m, preferably 0.005 to 0.3 ⁇ m. If the average major axial diameter exceeds 0.3 ⁇ m, the particle size is so large as to sometimes impair the surface smoothness. On the other hand, if the average major axial diameter is less than 0.005 ⁇ m, dispersion in the vehicle is unfavorably apt to be difficult. With due consideration of the dispersibility in the vehicle and the surface smoothness of the coated film, the preferable average major axial diameter is 0.02 to 0.2 ⁇ m.
• the average minor axial diameter of the acicular hematite particles used in the present invention is preferably 0.0025 to 0.15 ⁇ m. If the average minor axial diameter is less than 0.0025 ⁇ m, dispersion in the vehicle may be unfavorably difficult. On the other hand, if the average minor axial diameter exceeds 0.15 ⁇ m, the particle size is apt to become so large as to impair the surface smoothness. With due consideration of the dispersibility in the vehicle and the surface smoothness of the coated film, the more preferable average minor axial diameter is 0.01 to 0.10 ⁇ m.
• the BET specific surface area of the acicular hematite particle used in the present invention is preferably not less than 35 m 2 /g. If it is less than 35 m 2 /g, the acicular hematite particles may be coarse or sintering may be sometimes caused between particles, which are apt to exert a deleterious influence on the surface smoothness of the coated film.
• the BET specific surface area is more preferably not less than 40 m 2 /g, even more preferably not less than 45 m 2 /g.
• the upper limit of the BET specific surface area is ordinarily 300 m 2 /g. The upper limit is preferably 100 m 2 /g, more preferably 80 m 2 /g with due consideration of the dispersibility in the vehicle.
• the major axial diameter distribution of the acicular hematite particles used the present invention is preferably not more than 1.50 in geometrical standard deviation. If it exceeds 1.50, the coarse particles existent sometimes exert a deleterious influence on the surface smoothness of the coated film.
• the major axial diameter distribution is more preferably not more than 1.40, even more preferably not more than 1.35 in geometrical standard deviation with due consideration of the surface smoothness of the coated film. From the point of view of industrial productivity, the major axial diameter distribution of the acicular hematite particles is ordinarily 1.01 in geometrical standard deviation.
• the surfaces of the acicular hematite particles used in the present invention may be coated with at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon, if necessary.
• a hydroxide of aluminum an oxide of aluminum
• a hydroxide of silicon an oxide of silicon
• the amount of aluminum hydroxide, aluminum oxide, silicon hydroxide or silicon oxide as the coating material is preferably 0.01 to 50 wt % (calculated as Al or SiO 2 ) based on the total weight of the particles. If it is less than 0.01 wt %, the dispersibility improving effect derived by the coating material can hardly be obtained. If the amount exceeds 50.00 wt %, the coating effect becomes saturated, so that it is meaningless to add a coating material more than necessary. From the point of view of dispersibility in the vehicle, the preferable amount of coating material is 0.05 to 20 wt % (calculated as Al or SiO 2 ) based on the total weight of the particles
• acicular hematite particles coated with a coating material used in the present invention such as aspect ratio, average major axial diameter, average minor axial diameter, BET specific surface area, major axial diameter distribution, degree of densification (S BET /S TEM ) and resin adsorptivity are approximately equivalent in values to those of the acicular hematite particles used in the present invention the surfaces of which are not coated with a coating material.
• the acicular goethite particles obtained in this manner contain aluminum substantially uniformly from the central portions to the surfaces of the particles.
• the acicular goethite particles are heat-treated at a temperature as high as not less than 550° C.
• sintering preventives generally used are usable.
• phosphorus compounds such as sodium hexametaphosphate, polyphospholic acid and orthophosphoric acid
• silicon compounds such as #3 water glass, sodium orthosilicate, sodium metasilicate and colloidal silica
• boron compounds such as boric acid
• aluminum compounds including aluminum salts such as aluminum acetate, aluminum sulfate, aluminum chloride and aluminum nitride, alkali aluminate such as sodium aluminate, alumina sol and aluminum hydroxide
• titanium compounds such as titanyl sulfate may be exemplified.
• the amount of sintering preventive existent on the surfaces of the acicular hematite particles of the present invention is ordinarily not more than 10 wt %, preferably 0.05 to 10 wt % based on the total weight of the particles.
• an aluminum compound and/or a silicon compound is added to and mixed with an aqueous suspension under stirring which is obtained by dispersing the cake, slurry or dried particles of the acicular hematite particles into an aqueous solution.
• the pH value of the mixed solution is adjusted, if necessary.
• the acicular hematite particles thus coated with at least one selected from the group consisting of a hydroxide of aluminum, an oxide of aluminum, a hydroxide of silicon and an oxide of silicon are then filtered out, washed with water, dried and pulverized.
• the obtained acicular hematite particles may be further deaerated and compacted, if necessary.
• the same aluminum compounds as those described above as the sintering preventive are usable.
• the amount of aluminum compound added is 0.01 to 50.00 wt % (calculated as Al) based on the weight of the acicular hematite particles to be treated. If the amount is less than 0.01 wt %, the improvement of the dispersibility in the vehicle may be insufficient. On the other hand, if the amount exceeds 50.00 wt %, the coating effect becomes saturated, so that it is meaningless to add an aluminum compound more than necessary.
• the same silicon compounds as those described above as the sintering preventive are usable.
• the amount of silicon compound added is 0.01 to 50.00 wt % (calculated as SiO 2 ) based on the weight of the acicular hematite particles to be treated. If the amount is less than 0.01 wt %, the improvement of the dispersibility in the vehicle may be insufficient. On the other hand, if the amount exceeds 50.00 wt %, the coating effect becomes saturated, so that it is meaningless to add an silicon compound more than necessary.
• the amount thereof used is preferably 0.01 to 50.00 wt % (calculated as Al and SiO 2 ) based on the weight of the acicular hematite particles to be treated.
• the magnetic recording medium according to the present invention is produced by forming the non-magnetic undercoat layer formed on the non-magnetic substrate, forming a magnetic coating film on the non-magnetic undercoat layer by applying a coating composition containing magnetic iron-based metal particles, a binder resin and a solvent, and drying the coating film to obtain a magnetic recording layer.
• magnetic iron-based metal particles used in the present invention comprises iron and iron and at least one selected from the group consisting of Co, Al, Ni, P, Si, Zn, Ti, Cu, B, Nd, La and Y. Further, the following magnetic iron-based metal particles may be exemplified.
• Magnetic iron-based metal particles comprises iron and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 40 wt %, preferably 1.0 to 35 wt %, more preferably 3 to 30 wt % of cobalt (calculated as Co) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Nd, La and Y (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; ordinarily 0.05 to 40 wt %, preferably 1.0 to 35 wt %, more preferably 3 to 30 wt % of cobalt (calculated as Co) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Nd, La and Y (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; ordinarily 0.05 to 40 wt %, preferably 1.0 to 35 wt %, more preferably 3 to 30 wt % of cobalt (calculated as Co) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Nd, La and Y (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles.
• Magnetic iron-based metal particles comprises iron; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of aluminum (calculated as Al) based on the weight of the magnetic iron-based metal particles; ordinarily 0.05 to 40 wt %, preferably 1.0 to 35 wt %, more preferably 3 to 30 wt % of cobalt (calculated as Co) based on the weight of the magnetic iron-based metal particles; ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Nd, La and Y (calculated as the corresponding element) based on the weight of the magnetic iron-based metal particles; and ordinarily 0.05 to 10 wt %, preferably 0.1 to 7 wt % of at least one selected from the group consisting of Ni, P, Si, Zn, Ti, Cu and B (calculated as the corresponding element) based on the weight of the magnetic iron-
• the iron content in the particles is the balance, and is preferably 50 to 99 wt %, more preferably 60 to 95 wt % (calculated as Fe) based on the weight of the magnetic iron-based metal particles.
• the magnetic iron-based metal particles comprising (i) iron and Al; (ii) iron, Al and Co, (iii) iron, Al and at least one rare-earth metal such as Nd, La and Y, or (iv) iron, Al, Co and at least one rare-earth metal such as Nd, La and Y is preferable from the point of the durability of the magnetic recording medium. Further, the magnetic iron-based metal particles comprising iron, Al and at least one rare-earth metal such as Nd, La and Y is more preferable.
• any of these positions may be combined.
• magnetic iron-based metal particles uniformly containing aluminum from the core portion to the surface and coated with an aluminum-coating layer are more preferable.
• the content of aluminum is less than 0.05 wt % (calculated as Al)
• the adsorption of the resin to the magnetic iron-based metal particles in the vehicle may not be said sufficient, so that it may be difficult to improve the durability of the magnetic recording layer.
• the content of aluminum exceeds 10 wt %, the effect of improving the durability of the magnetic recording layer or the magnetic recording medium is observed, but the effect is saturated and it is meaningless to add aluminum more than necessary.
• the magnetic characteristics of the magnetic iron-based metal particles may be sometimes deteriorated due to an increase in the aluminum as a non-magnetic component.
• the existing amount of aluminum of the magnetic iron-based metal particles is preferably 0.1 to 7 % by weight (calculated as Al) based on the weight of the magnetic iron-based metal particles.
• magnetic recording medium of the present invention it is more preferable to produce a magnetic recording medium of the present invention using the magnetic iron-based metal particles containing Al, because the magnetic recording layer or magnetic recording medium produced is apt to have a more excellent durability.
• magnetic iron-based metal particles containing Al and rare-earth metal such as Nd, La and Y therein are the even more preferable.
• the acicular magnetic iron-based metal particles containing aluminum within the particles are produced, as is well known, by adding an aluminum compound at an appropriate stage during the above-described process for producing acicular goethite particles to produce acicular goethite particles containing aluminum at desired positions of the particles, and reducing at a temperature of 300 to 500° C., the goethite particles or the acicular hematite particles containing aluminum at desired positions within the particles which are obtained by dehydrating the goethite particles.
• the acicular magnetic iron-based metal particles coated with oxide of aluminum are produced by reducing at a temperature of 300 to 500° C., the acicular goethite particles coated with an oxide or hydroxide of aluminum, or the acicular hematite particles coated with the oxide or hydroxide of aluminum which are obtained by dehydrating the acicular goethite particles.
• the acicular magnetic iron-based metal particles used in the present invention have an average major axial diameter of ordinarily 0.01 to 0.50 ⁇ m, preferably 0.03 to 0.30 ⁇ m, more preferably 0.03 to 0.25 ⁇ m, an average minor axial diameter of ordinarily 0.0007 to 0.17 ⁇ m, preferably 0.003 to 0.10 ⁇ m, and an aspect ratio of ordinarily not less than 3:1, preferably and not less than 5:1.
• the upper limit of the aspect ratio is ordinarily 15:1, preferably 10:1 with the consideration of the dispersibility in the vehicle.
• the shape of the acicular magnetic iron-based metal particles may have not only acicular but also a spindle-shape, rice-ball shape or the like.
• the coercive force is preferably 1200 to 3200 Oe, more preferably 1500 to 3200 Oe, and the saturation magnetization is ordinarily preferably 100 to 170 emu/g, more preferably 130 to 170 emu/g with the consideration of the properties such as high-density recording.
• the resin adsorptivity of the acicular magnetic iron-based metal particles used in the present invention is ordinarily not less than 65%, preferably not less than 68%, more preferably not less than 70%, most preferably not less than 75%.
• the same binder resin as that used for the production of the non-magnetic undercoat layer is usable.
• the thickness of the magnetic recording layer obtained by applying the film-coating composition to the non-magnetic undercoat layer and dried is ordinarily in the range of 0.01 to 5.0 ⁇ m. If the thickness is less than 0.01 ⁇ m, uniform coating may be difficult, so that unfavorable phenomenon such as unevenness on the coating surface is observed. On the other hand, when the thickness exceeds 5.0 ⁇ m, it may be difficult to obtain desired signal recording property due to an influence of diamagnetism.
• the preferable thickness is in the range of 0.05 to 1.0 ⁇ m.
• the mixing ratio of the acicular magnetic iron-based metal particles with the binder resin in the magnetic recording layer is ordinarily 200 to 2000 parts by weight, preferably 300 to 1500 parts by weight based on 100 parts by weight of the binder resin.
• the magnetic recording medium according to the present invention has a coercive force of ordinarily 900 to 3500 Oe, preferably 1000 to 3500 Oe, more preferably 1500 to 3500 Oe; a squareness (residual magnetic flux density Br/saturation magnetic flux density Bm) of ordinarily 0.85 to 0.95, preferably 0.86 to 0.95, more preferably 0.87 to 0.95; a gloss (of the coating film) of ordinarily 180 to 300%, preferably 190 to 300%, more preferably 200 to 300%; a surface roughness Ra (of the coating film) of ordinarily not more than 14.0 nm, preferably 1.0 to 12.5 nm, more preferably 2.0 to 11.0 nm, even more preferably 2.0 to 10.0 nm, most preferably 2.0 to 9.0 nm; a Young's modulus (relative value to a commercially available video tape: AV T-120 produced by Victor Company of Japan, Limited) of ordinarily not less than 125, preferably not less than 130
• the running durability is ordinarily not less than 11 minutes, preferably not less than 15 minutes, more preferably not less than 18 minutes, still more preferably not less than 20 minutes.
• the running durability is ordinarily not less than 18 minutes, preferably not less than 20 minutes, more preferably not less than 22 minutes.
• the scratch resistance is ordinarily A or B, preferably A, when evaluated into four ranks: A (no scratch), B, C and D (great many scratches).
• the reason why the smooth surface of the non-magnetic undercoat layer and the strength of the substrate are enhanced is considered to be as follows. Since the binder resin adsorptivity of the non-magnetic particles in the vehicle is enhanced, as will be shown in later-described examples, the degree of adhesion of the non-magnetic particles in the non-magnetic undercoat layer or the non-magnetic undercoat layer itself to the non-magnetic substrate is enhanced.
• the reason why the durability of the surface of the magnetic recording medium is enhanced is not clear yet, but it is considered that the durability thereof is due to the synergistic effect of using the acicular hematite particles containing aluminum uniformly within the particles as the non-magnetic particles, and using the acicular magnetic iron-based metal particles as the magnetic particles.
• the resin adsorptivity of both the non-magnetic particles and the magnetic particles in the vehicles are enhanced due to the use of the above-described particles, as will be shown in later-described examples, the degree of adhesion of the non-magnetic particles in the non-magnetic undercoat layer or the non-magnetic undercoat layer itself to the non-magnetic substrate is enhanced, and the degree of adhesion of the magnetic particles in the magnetic recording layer and the magnetic recording layer itself to the non-magnetic undercoat layer is enhanced.
• the magnetic medium of the present invention having a non-magnetic undercoat layer using the hematite particles of the present invention has a small light transmittance, a smooth surface, a high strength and an excellent durability. That is, the magnetic medium is preferable as a high-density magnetic medium.
• the durability is more excellent. That is, the magnetic medium is preferable as a high-density magnetic medium.
• the average major axial diameter and the average minor axial diameter of the particles are expressed by the average values of 350 particles measured in the photograph obtained by magnifying an electron micrograph ( ⁇ 30000) by 4 times in the vertical and horizontal directions, respectively.
• the aspect ratio is the ratio of the average major axial diameter and the average minor axial diameter.
• the geometrical standard deviation ( ⁇ g) of particle size distribution of the major axial diameter was obtained by the following method.
• the major axial diameters of the particles were measured from the magnified electron microphotograph in the above-mentioned (1).
• the actual major axial diameters of the particles and the number of particles were obtained from the calculation on the basis of the measured values.
• On logarithmico-normal probability paper the major axial diameters were plotted at regular intervals on the abscissa-axis and the accumulative number of particles belonging to each interval of the major axial diameters was plotted by percentage on the ordinate-axis by a statistical technique.
• the major axial diameters corresponding to the number of particles of 50% and 84.13%, respectively, were read from the graph, and the geometrical standard deviation ( ⁇ g) was measured from the following formula:
• Geometrical standard deviation ( ⁇ g) ⁇ major axial diameter ( ⁇ m) corresponding to 84.13 % under integration sieve) ⁇ / ⁇ major axial diameter (geometrical average diameter) corresponding to 50% under integration sieve ⁇ .
• the specific surface area is expressed by the value measured by a BET method.
• S BET degree of denseness of the particles is represented by S BET /S TEM as described above.
• S BET is a specific surface area measured by the above-described BET method.
• S TEM is a value calculated from the average major axial diameter d cm and the average minor axial diameter w cm measured from the electron microphotograph described in (1) on the assumption that a particle is a rectangular parallellopiped in accordance with the following formula:
• ⁇ p is the true specific gravity of the hematite particles, and 5.2 g/cm 3 was used.
• S TEM is a specific surface area of a particle having a smooth surface without any dehydration pore within or on the surface thereof, the closer S BET /S TEM of particles is to 1, it means, the smoother surface the particles have without any dehydration pore within or in the surface thereof, in other words, the particles are high-density particles.
• the viscosity of the coating composition was obtained by measuring the viscosity of the coating composition at 25° C. at a shear rate D of 1.92 sec -1 by using an E type viscometer EMD-R (manufactured by Tokyo Keiki, Co., Ltd.).
• the resin adsorptivity of the particles represents the degree at which a resin is adsorbed to the particles. The closer to 100 the value obtained in the following manner, the better.
• the resin adsorption Wa was first obtained. 20 g of particles and 56 g of a mixed solvent (27.0 g of methyl ethyl ketone, 16.2 g of toluene, and 10.8 g of cyclohexanone) with 2 g of a vinyl chloride-vinyl acetate copolymer resin having a sodium sulfonate group dissolved therein were charged into a 100-ml polyethylene bottle together with 120 g of 3 mm ⁇ steel beads. The particles and the solvent were mixed and dispersed by a paint shaker for 60 minutes.
• a mixed solvent 27.0 g of methyl ethyl ketone, 16.2 g of toluene, and 10.8 g of cyclohexanone
• the coating composition was taken out, and charged into a 50-ml settling cylinder.
• the solid content was separated from the solvent portion by the a centrifugalization at a rate of 10000 rpm for 15 minutes.
• the concentration of the solid resin content contained in the solvent portion was determined by a gravimetric method and the resin content existing in the solid portion was determined by deducting the obtained resin content from the amount of the resin charged as the resin adsorption Wa (mg/g) to the particles.
• the total quantity of separated solid content was taken into a 100 ml-tall beaker, and 50 g of a mixed solvent (25.0 g of methyl ethyl ketone, 15.0 g of toluene, and 10.0 g of cyclohexanone) was added thereto.
• the obtained mixture was to ultrasonic dispersion for 15 minutes, and the thus-obtained suspension was charged into a 50-ml settling cylinder.
• the solid content was separated from the solvent portion by centrifuging them at a rate of 10000 rpm for 15 minutes.
• the concentration of the solid resin content contained in the solvent portion was measured so as to determine the resin content dissolved from the resin which had been adsorbed to the particle surfaces into the solvent phase.
• the surface roughness Ra is expressed by the average value of the center-line average roughness of the profile curve of the surface of the coating film by using "Surfcom-575A" (manufactured by Tokyo Seimitsu Co., Ltd.).
• the running durability was evaluated by the actual operating time under the conditions that the load was 200 gw and the relative speed of the head and the tape was 16 m/s by using "Media Durability Tester MDT-3000" (manufactured by Steinberg Associates). The longer the actual operating time, the higher the running durability.
• the scratch resistance was evaluated by observing through the microscope the surface of the magnetic tape after running and visually judging the degree of scratching. Evaluation was divided into the following four ranks.
• the strength of the coating film was expressed the Young's modulus obtained by "Autograph” (produced by Shimazu Seisakusho Ltd.).
• the Young's modulus was expressed by the ratio of the Young's modulus of the coating film to that of a commercially available video tape "AV T-120" (produce by Victor Company of Japan, Limited). The higher the relative value, the more favorable.
• the light transmittance is expressed by the linear adsorption coefficient measured by using "Photoelectric Spectrophotometer UV-2100" (manufactured by Shimazu Seisakusho, Ltd.).
• the linear adsorption coefficient is defined by the following formula, and the larger the value, the more difficult it is for the magnetic sheet to transmit light:
• FT represents thickness ( ⁇ m) of the coating composition of the film used for the measurement.
• the thickness (A) of a non-magnetic substrate was first measured.
• the thickness of the non-magnetic undercoat layer is expressed by B-A
• the thickness of the magnetic recording layer is expressed by C-B.
• the suspension containing FeCO 3 obtained by reacting an aqueous ferrous salt solution with an aqueous alkali carbonate solution, was oxidized by passing an oxygen-containing gas thereinto after aging the suspension.
• 1200 g of the thus-obtained acicular goethite particles was suspended in water so as to obtain a slurry, and the concentration of the solid content was adjusted to 8 g/liter.
• 150 liter of the slurry was heated to 60° C. and the pH value of the slurry was adjusted to 9.0 by adding a 0.1-N aqueous NaOH solution.
• the thus-obtained low-density spindle-shaped hematite particles containing aluminum had an average major axial diameter of 0.108 ⁇ m, an average minor axial diameter of 0.0161 ⁇ m, and an aspect ratio of 6.70.
• the BET specific surface area (S BET ) was 186.5 m 2 /g, the degree of densification (S BET /S TEM ) was 3.63.
• the Al content was 4.27 wt %, the geometrical standard deviation was 1.35 and the resin adsorptivity was 68.8%.
• the hematite particles were used as the non-magnetic particles for a later-described non-magnetic undercoat layer A.
• 850 g of the low-density spindle-shaped hematite particles were then charged into a ceramic rotary furnace, and heat-treated in the air at 650° C. for 30 minutes while rotating the furnace so as to fill in dehydration pores.
• 100 g of the high-density spindle-shaped hematite particles obtained were charged into 1 liter of pure water and peptized by a homomixer (produced by Tokushu-kika Kogyo, Co., Ltd.), then filtered through a Buchner filter, and pure water was passed until the electric conductivity of the filtrate became not more than 30 ⁇ s. The particles were then dried and pulverized to obtain high-density spindle-shaped hematite particles.
• the thus-obtained high-density spindle-shaped hematite particles had an average major axial diameter of 0.107 ⁇ m, an average minor axial diameter of 0.0162 ⁇ m, and an aspect ratio of 6.60.
• the BET specific surface area (S BET ) was 58.0 m 2 /g, the degree of densification (S BET /S TEM ) was 1.14 and the geometrical standard deviation was 1.36.
• the Al content was 4.30 wt % and the resin adsorptivity was 71.6%.
• the hematite particles were used as the non-magnetic particles for a later-described non-magnetic undercoat layer B.
• cyclohexanone methyl ethyl ketone and toluene
• the thus-obtained coating composition containing hematite particles was as follows:
• the viscosity of the obtained respective coating composition was 384 cP.
• the respective coating composition obtained was applied to a polyethylene terephthalate film of 12 ⁇ m thick to a thickness of 55 ⁇ m by an applicator, and the film was then dried, thereby forming a non-magnetic undercoat layer.
• the thickness of the non-magnetic undercoat layer was 3.5 ⁇ m.
• the non-magnetic undercoat layer A produced from the low-density spindle-shaped hematite particles as the non-magnetic particles had a gloss of 189%, and a surface roughness Ra of 11.0 nm.
• the Young's modulus (relative value) of the substrate was 132.
• the non-magnetic undercoat layer B produced from the high-density spindle-shaped hematite particles as the non-magnetic particles had a gloss of 215%, and a surface roughness Ra of 7.6 nm.
• the Young's modulus (relative value) of the substrate was 135.
• cyclohexanone
• the thus-obtained magnetic coating composition was as follows:
• the magnetic coating composition obtained was applied to the non-magnetic undercoat layer A or B to a thickness of 15 ⁇ m by an applicator, and the magnetic recording medium obtained was oriented and dried in a magnetic field, and then calendered. The magnetic recording medium was then subjected to a curing reaction at 60° C. for 24 hours, and thereafter slit into a width of 0.5 inch, thereby obtaining a magnetic tape.
• the thickness of the magnetic recording layer was 1.1 ⁇ m.
• the coercive force Hc of the magnetic tape produced by forming a magnetic recording layer on the non-magnetic undercoat layer A was 1961 Oe, the squareness (Br/Bm) thereof was 0.87, the gloss thereof was 199%, the surface roughness Ra thereof was 10.0 nm, the Young's modulus (relative value) thereof was 134, the linear absorption coefficient thereof was 1.25, the running durability thereof was 23.6 minutes, and the scratch resistance thereof was A.
• the coercive force Hc of the magnetic tape produced by forming a magnetic recording layer on the non-magnetic undercoat layer B was 1973 Oe, the squareness (Br/Bm) thereof was 0.88, the gloss thereof was 221%, the surface roughness Ra thereof was 7.8 nm, the Young's modulus (relative value) thereof was 135, the linear absorption coefficient thereof was 1.26, the running durability thereof was 29.6 minutes, and the scratch resistance thereof was A.
• Acicular hematite particles containing aluminum uniformly within the particles which were different in the basic production reaction of the acicular goethite particles containing aluminum uniformly within the particles as the starting material, aluminum content, kind and amount of sintering preventive, degree of densification, presence or absence of a surface coating, kind and amount of surface coating, and resin adsorptivity were prepared.
• the surfaces of the acicular non-magnetic particles were coated in the following manner except for varying the kind of non-magnetic particles, and the kind and amount of coating material.
• Non-magnetic undercoat layers were obtained in the same was as in Example 1 by using the non-magnetic particles A1 to A9.
• Magnetic media using the magnetic iron-based metal particles were produced in the same way as in Example 2 except for the kind of non-magnetic undercoat layer and the kind of acicular magnetic iron-based metal particles.

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• 1997
  • 1997-02-28 JP JP9062020A patent/JPH10241148A/ja active Pending
• 1998
  • 1998-02-26 EP EP98301409A patent/EP0862163B1/de not_active Expired - Lifetime
  • 1998-02-26 US US09/030,962 patent/US6054201A/en not_active Expired - Fee Related
  • 1998-02-26 DE DE69802855T patent/DE69802855T2/de not_active Expired - Fee Related

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